Alkylhalopentenyl sulfides



United States PatentO ALKYLHALOPENTENYL SULFIDES Earl WilliamLane,Philadelphia, Pa., assignor to llohm & Haas Company, Philadelphia, Pa.,a corporation of Delaware No Drawing. Application July 19, 1955 SerialNo. 526,076

12 Claims. (Cl. 260-609) This invention relates to alkylhalopentenylsulfides as new compositions of matter. method of preparation of thesealkylhalopentenyl sulfides.

The present invention is concerned with the preparation ofalkylhalopentenyl sulfides by reacting the corresponding alkylhalomethylsulfides with butadiene in the presence of a Friedel-Crafts catalyst.The alkylhalopentenyl sulfides of the present invention may berepresented by the formula RSCH CH CH=CHCH X, in which R is an alkylgroup of one to eighteen carbon atoms and X is either chlorine orbromine.

This application is a continuation-in-part of, my copending applicationSerial Number 443,153, filed July 13, 1954, now abandoned. I

The starting compounds employed in the instant method, thealkylhalomethyl sulfides, are known and usually prepared by thehalomethylation of a thioalcohol.

The present method concerns the reaction between an alkylhalomethyl'sulfide and butadiene, in a one-to-one ratio, to form analkylhalopentenyl sulfide having the formula RSCH CH CH=CHCH X, definedabove. T ypical of the alkyl groups that may be employed as R aremethyl, ethyl, propyl, butyl, isobutyl, hexyl, octyl, isooctyl,tert-octyl, nonyl, decyl, isodecyl, tert-decyl, dodecyl, tetradecyl, andoctadecyl. The'Xin the formula may represent chlorine or bromine.Chlorine compounds are more readily available and somewhat lessexpensive than the corresponding bromine compounds and arethereforeusually preferred. I i

The subject reaction is usually conducted at temperatures determined.largely .by the exothermic nature of the reaction itself. The heat ofreaction, though not usually 7 great, will cause the temperature of thereaction, mixture to rise from room temperature to about to C. within arelatively short time. The reaction will satisfactorily occur inthetemperature range ore-10 to 80 C., with the preferred range beingabout +10 to C. Actually, the reaction will occur above 80 C. but, asthe temperature is progressively raised, the danger of undesirable sidereactions increases. At these high temperatures there is the possibilitythat polymerization of the butadiene may occur. There is furtherpossibility that other undesirable'side reactions may occur. In order tominimize and substantially eliminate the occurrence of reactions otherthan the principal one, the range of temstantial part of the reactionoceurs in the shorter periods of time.

Atmospheric pressure is usually employed, largely as a matter ofconvenience. Pressure greater than atmospheric may be advantageouslyused with some improvements in yields usually observed; I Apparently,pressures greater It further relates to a preferred range.

'may be employed are aluminum chloride, zinc chloride,

ice

than atmospheric tend to keep the butadiene in the reaction mediumlonger and to restrict its premature exit from the proximity ofitscoreactant, the alkylhalomethyl sulfide. desirable to utilize more fullythe butadiene which at the same time tends to increase the yield of theproduct.

A catalyst of the Friedel-Crafts type is needed in order to obtain anappreciable yield of product. The amount of catalyst used may bevariedfrom about 0.5 to 15% by weight, the higher amounts generally causinghigher yields,

although sometimes at the uppermost part of the range the additionalamounts of catalyst elfect a minimal increase in yield. Usually, about1% to 10%, by Weight, of catalyst produces satisfactory results and suchis the Typical of the indivdual catalysts that zinc. bromide, ferricchloride, titanium tetrachloride,

stannic chloride, zinc stearate, and the like. In addition to ,aFriedel-Crafts catalyst, there may be present, in order to acceleratethe reaction, glacial acetic acid, glacial formic acid, or the like.

If it is desired, a solvent may be employed although such is notnecessary. The need or desire for a solvent is minimized by the use of.glacial acetic acid, glacial formic acid, or the like since such servesas a solvent as well as an accelerator. If a solvent is desired, theremay be used chloroform, ethylene dichloride, or other common chlorinatedsolvents.

The butadiene used in the instant reaction is introduced at anyconvenient rate, preferably at a rate that minimizes waste of materials.It is desirable that the butadiene be in slight excess in order to favorthe principal reaction. However, a large excess should be avoided inorder to prevent undesirable side reactions.

Compounds'having a chemical configuration similar to that of butadienemay be employed in place of the butadiene to form similar products,although usually in reduced yields. Among the compounds that may besatisfactorily used are isoprene, hexadiene, cyclopentadiene, and thelike.

At the conclusion of the reaction, after the alkylhalopentenyl sulfidehas been formed, the reaction mixture is washed with water, aqueous 10%sodium carbonate, and

water again. Solvent, water, and unreacted components are removed bystripping, and the product is distilled, preferably at reduced pressuresdown to about 0.5mm.

The alkylhalopentenyl sulfides .arc liquid products that are useful asfungicides. The present compounds are particularly effective againstStemphylium sarcinacforme and Monilinia fructicola in concentrations aslow as 0.1% as demonstrated in standardfungicide tests. Thealkylhalopentenyl sulfides may be reacted with sodium, potassium,orammonium thiocyanate to form bactericidal and fungicidal compounds.They may be quaternized with trimethylamine or benzyldimethylamine toform bactericidal compounds effective against Micrococcus pyrogenes var.

aureus and Salmonella typhosa. These sulfides may be reacted with sodiumsulfite to yield effective dishwashing detergents. Thesealkylhalopentenyl sulfides may be reacted with alkyl mercaptans to formcompounds useful as lubricating oil additives in the field of corrosionand oxidation inhibitors.

The method of making the alkylhalopentenyl sulfides according to thepresent invention is shown in the following illustrative examples inwhich throughout.

Example 1 There were added parts of methylchloromethyl sulfide, 10 partsof anhydrous zinc chloride, and parts of glacial acetic acid to athree-necked flask equipped with a thermometer, stirrer, gas-dispersiontube, and

Therefore, the elevated pressures are frequently parts by weight areused water-cooled condenser fitted with a calcium chloride drying tube.To this mixture there was added 60 parts of butadiene over a period ofabout minutes. Stirring of the reaction mixture was continued during thebutadiene 'additi'on. Ant exothermic reaction was. observed and thetemperature of the reaction mixture rose to C. in about two hours.Stirring of the reaction was. continued, for 16 additional hours duringwhich. time the heat, of reaction. gradually dissipated. The reactionmixture was washed with water twice, twice with aqueous 10% sodiumcarbonate, and once more with water. It was dried over anhydrous.magnesium sulfate, filtered,.stripped of light volatile components, andthen distilled. The liquid product corresponded to methylchloropentenylsulfide.

Example 2 There were added to a reaction vessel 120 parts ofbutylchloromethylsulfide, 10, parts of anhydrous zinc stcarate, andpartsof glacial formic acid. Buta-. diene, in the amount of 62 parts, wasintroduced during a period of about 12 minutes, while the mixture wasstirred: "An exothermic reaction was noticed, the heat from which wasgradually dissipated by continued stirring over a perieod of six hours.The reaction mixture was washed twice with water, twice with aqueous 10%sodium carbonate, and once more with water. It was dried over anhydrousmagnesium sulfate, filtered, stripped of light, volatile components, anddistilled. The liquid product corresponded to butylchloropentenylsulfide.

Similarly, there was made isobutylchloropentenyl sulfidc.

Example 3 To a mixture of 140 parts of octylchloromethyl sulfide, 10parts of anhydrous zinc chloride, and parts of glacial acetic acid therewas added over a period of 20 minutes 70 parts of butadiene. The mixturewas stirred during the addition of the butadiene and thereafter, duringwhich time an exothermic reaction was noticed causing the temperature torise to 38 C. Stirring was continued for 18 hours and the heatofreaction was gradually dissipated. The reaction mixture waswashedtwice with water, twice with aqueous 10% sodium carbonate, and onceagain with water. It was dried over anhydrous magnesium sulfate,filtered, stripped of light volatile components, and thendistilled. Theliquid product was identified= as octylchloropentenyl sulfide. 1

In like manner there was prepared octylbromopentenyl sulfide.

Example 4 There were added together in a reaction vessel 159 parts'ofdodecylchloromethyl sulfide, 12 parts of anhydrous zinc chloride, and.parts of glacial acetic acid. Butadiene was introduced into the mixture,in the amount of 60 parts, over a period of-lO minutes. The mixture wasstirred during thegbutadiene addition and thereafter for, a period of 20hours. Anexothermic reaction was observed which caused the temperatureto rise gradually to 35 C. Continued stirring during the period of 20hours aided in the dissipation of the heat of reaction which caused the,temperature. to gradually subside and return to room temperature. The.reaction mixture was. washed twice with water, twice with aqueous 10%sodium carbonate, and once more with water. The reaction. mixture was.then dried over anhydrous magnesium sulfate, filtered, stripped of lightvolatile components, and then distilled. The liquid product distilled at151 to 175 C. at 1.2 mm. and had a sulfur content of 9.8% (10.5%theoretical) and a chlorine content of 11.0% (11.6% theoretical). Theproduct was identified as. dodecylchloropentenyl sulfide.

4 Example 5 There were mixed together in a reaction vessel 252 parts ofoctadecylchloromethyl sulfide, 15 parts of anhydrous zinc stearate, andparts of glacial formic acid. Over a period of 15 minutes 70 parts ofbutadiene was added during which time the reaction mixture was stirred.Thereafter, stirring was continued for 16 hours, after which thereaction mixture was washed twice with Water, twice with aqueous 10%sodium carbonate, and once again with water. The mixture was then driedover anhydrous magnesium carbonate, filtered, stripped of light volatilecomponents, and distilled. The product was identified asoctadecylchloropentenyl sulfide.

I claim:

1. A method for preparing compounds having the formula RSCH CH CH=CHCH Xwhich comprises reacting with. butadiene, in the presence of aFriedel-Crafts. catalyst, compounds having the formula RSCI-I X, inwhich R is an alkyl group of one to eighteen. carbon atoms and. X is amember of the Class consisting. of chlorine and bromine.

2. A method. for preparing compounds having the formula RSCH CH CH CHCHX which comprises reacting with butadiene, in the temperature range of+10 to 60 C. in, the presence of a Friedel-Crafts catalyst and glacialacetic acid, compounds. having the formula RSCH CI, in which R is analkyl group of one to eighteen carbon atoms, and separating the product.

4. A method for preparing which comprises reacting butadiene with C HSCH' CI in the temperature range of +10 to 60 C. in the presence of aFriedel-Crafts catalyst and glacial acetic acid.

5. A method for preparing which comprises reacting butadiene withCQHIQSCHZCI in the temperature range of +10 to 60 C. in the presence ofa Friedel-Crafts catalyst and glacial acetic acid.

6. A method for preparing which. comprises reacting butadiene withCIQHZBSCHQCI in the temperature range of +10 to 60 C. in the presence,of a. Friedel-Crafts catalyst and glacial acetic acid.

7. As new compositions of matter, compounds having; the formula in whichR is an alkyl group of one to eighteen carbon atoms-and-"X is a memberof the class consisting of chlorine and bromine.

8. Asnew compositions of matter, compounds having the formula RSCH CH CH-CHCH CI 5 in which R is an alkyl group of one to eighteen carbon atoms.I

9. As new compositions of matter, compounds having the formula in whichR is an alkyl group of one to eighteen carbon atoms.

10. As a new composition of matter,

C3H17SCH3CH3CH=CHCH2Cl 11. As a new composition of matter,

C.H ,SCH CH,CH=CHCH,Cl

12. As a new composition of matter,

References Cited in the file of this patent UNITED STATES PATENTS

1. A METHOD FOR PREPARING COMPOUNDS HAVING THE FORMULA
 7. AS NEWCOMPOSITIONS OF MATTER, COMPOUNDS HAVING THE FORMULA